CN102689949A - Method for electrolytic disinfection of recirculated cooling water - Google Patents
Method for electrolytic disinfection of recirculated cooling water Download PDFInfo
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- CN102689949A CN102689949A CN2011100728481A CN201110072848A CN102689949A CN 102689949 A CN102689949 A CN 102689949A CN 2011100728481 A CN2011100728481 A CN 2011100728481A CN 201110072848 A CN201110072848 A CN 201110072848A CN 102689949 A CN102689949 A CN 102689949A
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Abstract
The invention relates to a method for electrolytic disinfection of recirculated cooling water. The method is characterized in that an electrolytic current is controlled according to a chloride ion concentration and a chemical oxygen demand (COD) value of recirculated cooling water so that a concentration of an electrolysate is kept in a required range and thus it is guaranteed that a concentration of an electrolysate reaches to a required value and it is avoided that because of an over-high concentration of an electrolysate, harmful effects are produced.
Description
Technical field
The present invention relates to a kind of electrolytic sterilizing method of recirculated cooling water.
Background technology
In the industrial circulating cooling water system; The enrichment method of nutrient is that microbial growth has been created advantageous conditions with suitable water temperature; If do not control; Mikrobe will breed and produce the large number of biological foundry loam rapidly, and foundry loam causes reduction and the pipeline and the corrosion on Equipment of thermo-efficiency attached on pipeline and the cooling apparatus.
The control method of mikrobe mainly contains chemical method and physics method.The most frequently used method is a chemical method, promptly comes controlling microbial through in water, adding various chemical agents.The chemical method cost is low, effective, but chemical method also has the water quality deterioration of making, complicated operating process, can not adapt to change of water quality well, to shortcoming such as environment is unfriendly.The physics method is meant the method for physical means controlling microbial such as adopting ultraviolet ray, UW.The physics method is environmentally friendly, but nothing continues germicidal action and effect is undesirable.
Electrolytic process is the method through the electrolysis controlling microbial.The physical action of electrolytic process has direct sterilizing ability, but sterilization rate is lower, and it mainly is to come germ-resistant through the chemical action of electrolysate.The characteristics that electrolytic process has environmental friendliness, less investment, flexible operation and easily is automated.
The principle that electrolytic process is carried out germicidal treatment is; Contain a certain amount of cl ions in the water coolant; Its concentration range is at 20mg/L-2000mg/L, and when adopting electrolytic process to handle water coolant, the cl ions in the water will be oxidized to reactive chlorine; And reactive chlorine is the good sterilization agent, can directly carry out sterilization to water coolant.When adopting electrolytic process that water coolant is carried out germicidal treatment; For guaranteeing sterilization effect; Should keep higher residual chlorine concentration (effective chlorine density), but the too high meeting of residual chlorine concentration causes pipeline and corrosion on Equipment in the cooling water system, therefore need the residual chlorine concentration in the water be controlled in the suitable scope.Yet the residual chlorine concentration in the water coolant is not only relevant with the reactive chlorine generation rate, and how effectively the residual chlorine concentration in the controlled chilling water is the difficult problem that the present technique field faces.
Summary of the invention
The invention provides a kind of electrolytic sterilizing method of recirculated cooling water, this method can be controlled the residual chlorine concentration in the water effectively.
Method provided by the invention comprises: water coolant is imported electrolyzer carry out electrolysis treatment, the water coolant after the processing returns cooling water recirculation system, calculates the Faradaic current value according to the following steps, and the Faradaic current of electrolyzer is adjusted to calculated value;
(1) according to the water coolant COD value of target residual chlorine concentration and mensuration, by (I) formula calculated activity chlorine generation rate;
The reactive chlorine generation rate=(target residual chlorine concentration+c * COD)/b (I)
Wherein, the unit of residual chlorine concentration is mg/L, and the unit of reactive chlorine generation rate is g/h, and the unit of COD is mg/L, and the constant that b is relevant with blowdown flow rate, water quality and the temperature of water coolant, c are the constant of numerical value between 0.06～0.20;
(2) according to the chlorine ion concentration of step (1) activity calculated chlorine generation rate and mensuration, calculate the Faradaic current value by (II) formula;
Faradaic current=reactive chlorine generation rate/(a * chlorine ion concentration) (II)
Wherein, the unit of chlorine ion concentration is mg/L, and the unit of electric current is A, and a is and electrode size, material, the relevant constant of interelectrode distance.
Among the present invention, constant a can rule of thumb confirm, also can confirm according to following method:
Adopt with recirculating cooling water system in the identical device of electrolyzer that uses make an experiment, to reach specific conductivity firmly identical with water coolant but do not contain COD for chlorine ion concentration, calcium in the test water, blowdown flow rate is 0, test temperature is identical with recirculating cooling water system; By formula (III) computational constant a:
A=(residual chlorine concentration * test Total Water)/(Faradaic current * chlorine ion concentration * electrolysis time) (III)
Wherein, the unit of chlorine ion concentration is mg/L, and the unit of electric current is A, and the unit of electrolysis time is hour, and the unit of residual chlorine concentration is mg/L, and the unit of test Total Water is m
3
In the method for confirming constant a, electrolysis time is preferably 0.5～2 hour.
Among the present invention, constant b can confirm according to following method:
Adopt the electrolyzer in the cooling water recirculation system that runs well to confirm constant b, analyze the residual chlorine concentration under chlorine ion concentration, COD value and the certain electric current in the water coolant, according to current value and chlorine ion concentration, (IV) calculates the reactive chlorine generation rate by formula;
Reactive chlorine generation rate=a * chlorine ion concentration * Faradaic current (IV)
B=reactive chlorine generation rate/(target residual chlorine concentration+c * COD) (V)
(V) scope of constant c is between 0.06～0.20 in, and the COD value according to reactive chlorine generation rate and water coolant calculates constant b by formula V.
The present invention does not have special requirement to electrolyzer, and those skilled in the art can design or buy electrolyzer as the case may be easily voluntarily.Under the preferred situation, in the electrolyzer of the present invention, the body material of electrode is a titanium, and the surface is coated with one or more in metal platinum, iridium, ruthenium, tantalum, the palladium, one or more in the perhaps above-mentioned MOX; Under the preferred situation, in the electrolyzer of the present invention, employed electrode is Ti/RuO
2-TiO
2Electrode and/or Ti/IrO
2-Ta
2O
5Electrode.Among the present invention, negative electrode can be identical with the anodic electrode materials, also can be different.
Among the present invention, in the said recirculated cooling water, chlorine ion concentration is preferably 20mg/L～2000mg/L.
The present invention finds that on the basis of test the reactive chlorine generation rate is relevant with the chlorine ion concentration and the Faradaic current of water coolant, and the concentration of chlorine residue is not only relevant with the reactive chlorine generation rate, and is also relevant with the COD value of water coolant.Therefore the present invention proposes to analyze chlorine ion concentration and COD value in the water coolant, sets Faradaic current according to the target residual chlorine concentration of analytical results and system, thereby the generation rate of control reactive chlorine reaches the target residual chlorine concentration.
Description of drawings
Fig. 1 is applied to the schematic flow sheet of cooling water system for the present invention.
Fig. 2 confirms the experiment process figure of constant a for the present invention.
Among the figure, 1 is cooling tower, and 2 is water pump, and 3 is electrolyzer, and 4 is electrolyzer, and 4A and 4B are electrode, and 5 is power supply, and 6 is storage tank, and 7 is water pump.
Embodiment
Further specify embodiment of the present invention below in conjunction with Fig. 1 and Fig. 2.
Fig. 1 is applied to the schematic flow sheet of cooling water system for the present invention.Electrolyzer 3 comprises electrolyzer 4 and is arranged on electrode 4A in 4,4B and applies the power supply 5 of voltage to 4A, 4B.Water coolant in the water collecting basin of cooling tower 1 below is sent into electrolyzer 4 by pump 2, in this electrolyzer, carries out electrolysis treatment.Brine electrolysis after the processing is sent the water collecting basin of cooling tower 1 below back to.
Fig. 2 is the experiment process figure of the present invention for coefficient a in analysis (1) formula.Electrolyzer 3 is identical with Fig. 1.Water in the storage tank 6 is sent into electrolyzer 4 by pump 7, in this electrolyzer, carries out electrolysis treatment.Brine electrolysis after the processing is sent storage tank 6 back to.It is identical that the chlorine ion concentration of test water, calcium reach among specific conductivity and Fig. 1 water coolant firmly, but the COD value of test water is zero.
Residual chlorine concentration through following method is kept in the water coolant is stable:
(1) confirms constant a and b according to preceding method;
(2), confirm the residual chlorine concentration that to keep in the water coolant according to the requirement of cooling circulating water system;
(3) chlorine ion concentration and COD value in the periodic analysis water coolant, according to the Faradaic current value that preceding method calculating needs are kept, the Faradaic current of regulating the electrolyzer among Fig. 1 is a calculated value.
Below specify the present invention through embodiment.
Embodiment 1
Certain recirculating cooling water system is carried out electrolytic sterilizing, and flow process is as shown in Figure 1, and quantity of circulating water is 100m
3/ h, this cooling water system target residual chlorine concentration is 0.4mg/L, moves 31 days continuously.
At first, the chlorine ion concentration of analyzing in the water coolant is 200mg/L, and the COD value is 100mg/L.
Secondly, ask coefficient a, confirm the relation of reactive chlorine generation rate and electric current and chlorine ion concentration.Set up testing apparatus as shown in Figure 2, the chlorine ion concentration in the test water is 200mg/L for this reason, and COD is 0mg/L, and it is identical with water coolant that calcium reaches specific conductivity firmly, and the test water yield is 10m
3, operation 1h.
The setting Faradaic current is 10A; The residual chlorine concentration that records is 0.2mg/L, according to residual chlorine concentration, the test water yield and working time calculated activity chlorine generation rate be 2g/h, with current value, chlorine ion concentration, reactive chlorine generation rate substitution (III) formula; Constant c value gets 0.1, tries to achieve coefficient a=0.001.Therefore the relation of reactive chlorine generation rate and electric current and chlorine ion concentration is:
Reactive chlorine generation rate (g/h)=0.001 * chlorine ion concentration (mg/L) * electric current (A)
Then, in the actual device of Fig. 1, move, when bringing into operation; Still setting electric current is 10A; Record after stable that residual chlorine concentration is 0.2mg/L in the water coolant, trying to achieve the reactive chlorine generation rate according to following formula is 2g/h, with COD value, residual chlorine concentration, reactive chlorine generation rate substitution (V) formula; Try to achieve coefficient b=5.1, so the relation of residual chlorine concentration and reactive chlorine generation rate and COD value is:
Residual chlorine concentration (mg/L)=5.1 * reactive chlorine generation rate (g/h)-0.1 * COD (mg/L)
During commencement of commercial operation, the water quality of analyzing water coolant is following: chlorine ion concentration is 200mg/L, and the COD value is 100mg/L, is 0.4mg/L for making the target residual chlorine concentration, and the reactive chlorine generation rate should be 2.04g/h, and set Faradaic current is 10.2A for this reason.Afterwards, analyzed chlorine ion concentration and the COD value in the primary water in per 5 days, and according to analytical results adjustment Faradaic current.Test-results is seen table 1.
Table 1
Can find out that from table 1 in implement to move by the present invention 31 days, the actual residual chlorine concentration that records can maintain in the scope of 0.3-0.5mg/L.In addition, run duration is provided with the carbon steel test piece in recirculating cooling water system, and the average corrosion rate that records in 31 days is 20mdd.
Certain recirculating cooling water system is carried out electrolytic sterilizing, and flow process is as shown in Figure 1, and quantity of circulating water is 80m
3/ h, this cooling water system target residual chlorine concentration is 0.3mg/L, moves 31 days continuously.
At first, the chlorine ion concentration of analyzing in the water coolant is 150mg/L, and the COD value is 80mg/L.
Secondly, ask coefficient a, confirm the relation of reactive chlorine generation rate and electric current and chlorine ion concentration.Adopt the testing apparatus identical with embodiment 1, because a relevant with electrode size, material, interelectrode distance, so coefficient a=0.001.The relation of reactive chlorine generation rate and electric current and chlorine ion concentration is:
Reactive chlorine generation rate (g/h)=0.001 * chlorine ion concentration (mg/L) * electric current (A)
Then, in the device of Fig. 1, move, when bringing into operation; The setting electric current is 8A, and the residual chlorine concentration that records in the water coolant after stablizing is 0.2mg/L, and trying to achieve the reactive chlorine generation rate according to following formula is 1.2g/h; With COD value, residual chlorine concentration, reactive chlorine generation rate, substitution (V) formula, the c value gets 0.15; Try to achieve coefficient b=6.8, so the relation of residual chlorine concentration and reactive chlorine generation rate and COD value is:
Residual chlorine concentration (mg/L)=6.8 * reactive chlorine generation rate (g/h)-0.15 * COD (mg/L)
The water quality of analyzing water coolant during commencement of commercial operation is following: chlorine ion concentration is 150mg/L, and the COD value is 80mg/L, is 0.3mg/L for making the target residual chlorine concentration, and the reactive chlorine generation rate should be 1.81g/h, and set Faradaic current is 12.1A for this reason.Afterwards, analyzed chlorine ion concentration, COD value in the primary water in per 5 days, and according to analytical results adjustment Faradaic current.Test-results is seen table 2.
Table 2
Can find out that from table 2 in implement to move by the present invention 31 days, the actual residual chlorine concentration that records can maintain in the scope of 0.2-0.4mg/L.In addition, run duration is provided with the carbon steel test piece in recirculating cooling water system, and the average corrosion rate that records in 31 days is 15mdd.
Claims (6)
1. the electrolytic sterilizing method of a recirculated cooling water; Comprise: water coolant is imported electrolyzer carry out electrolysis treatment; Water coolant after the processing returns cooling water recirculation system, calculates the Faradaic current value according to the following steps, and the Faradaic current of electrolyzer is adjusted to calculated value;
(1) according to the water coolant COD value of target residual chlorine concentration and mensuration, by (I) formula calculated activity chlorine generation rate;
The reactive chlorine generation rate=(target residual chlorine concentration+c * COD)/b (I)
Wherein, the unit of residual chlorine concentration is mg/L, and the unit of reactive chlorine generation rate is g/h, and the unit of COD is mg/L, and the constant that b is relevant with blowdown flow rate, water quality and the temperature of water coolant, c are the constant of numerical value between 0.06～0.20;
(2) according to the chlorine ion concentration of step (1) activity calculated chlorine generation rate and mensuration, calculate the Faradaic current value by (II) formula;
Faradaic current=reactive chlorine generation rate/(a * chlorine ion concentration) (II)
Wherein, the unit of chlorine ion concentration is mg/L, and the unit of electric current is A, and a is and electrode size, material, the relevant constant of interelectrode distance.
2. according to the described method of claim 1, it is characterized in that constant a confirms according to following method:
Adopt with recirculating cooling water system in the identical device of electrolyzer that uses make an experiment, to reach specific conductivity firmly identical with water coolant but do not contain COD for chlorine ion concentration, calcium in the test water, blowdown flow rate is 0, test temperature is identical with recirculating cooling water system; By formula (III) computational constant a:
A=(residual chlorine concentration * test Total Water)/(Faradaic current * chlorine ion concentration * electrolysis time) (III)
Wherein, the unit of chlorine ion concentration is mg/L, and the unit of electric current is A, and the unit of electrolysis time is hour, and the unit of residual chlorine concentration is mg/L, and the unit of test Total Water is m
3
3. according to the described method of claim 1, it is characterized in that constant b confirms according to following method:
Adopt the electrolyzer in the cooling water recirculation system that runs well to confirm constant b, analyze the residual chlorine concentration under chlorine ion concentration, COD value and the certain electric current in the water coolant, according to current value and chlorine ion concentration, (IV) calculates the reactive chlorine generation rate by formula;
Reactive chlorine generation rate=a * chlorine ion concentration * Faradaic current (IV)
B=reactive chlorine generation rate/(target residual chlorine concentration+c * COD) (V)
COD value according to reactive chlorine generation rate and water coolant calculates constant b by formula V.
4. according to the described method of claim 1, it is characterized in that in the said electrolyzer, the body material of electrode is a titanium, the surface is coated with one or more in metal platinum, iridium, ruthenium, tantalum, the palladium, one or more in the perhaps above-mentioned MOX.
5. according to the described method of claim 4, it is characterized in that in the said electrolyzer, electrode is Ti/RuO
2-TiO
2Electrode and/or Ti/IrO
2-Ta
2O
5Electrode.
6. according to the described method of claim 1, it is characterized in that in the said recirculated cooling water, chlorine ion concentration is 20mg/L～2000mg/L.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058336A (en) * | 2013-01-24 | 2013-04-24 | 沈阳惠丰环境科技有限公司 | Direct-current electrolytic treatment process and equipment for circulating cooling water |
| CN104556311A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Circulating cooling water sterilizing method and application |
| CN105819594A (en) * | 2015-01-09 | 2016-08-03 | 中国石油化工股份有限公司 | Recirculated cooling water processing method |
| CN115636479A (en) * | 2021-07-19 | 2023-01-24 | 重庆美的制冷设备有限公司 | Purifying equipment, control method and device thereof and storage medium |
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Patent Citations (4)
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| US4767511A (en) * | 1987-03-18 | 1988-08-30 | Aragon Pedro J | Chlorination and pH control system |
| CN101068750A (en) * | 2004-11-29 | 2007-11-07 | 赛温德罗有限公司 | System and method for treatment of ballast water |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058336A (en) * | 2013-01-24 | 2013-04-24 | 沈阳惠丰环境科技有限公司 | Direct-current electrolytic treatment process and equipment for circulating cooling water |
| CN103058336B (en) * | 2013-01-24 | 2014-10-22 | 沈阳惠丰环境科技有限公司 | Direct-current electrolytic treatment process and equipment for circulating cooling water |
| CN104556311A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Circulating cooling water sterilizing method and application |
| CN104556311B (en) * | 2013-10-22 | 2018-09-28 | 中国石油化工股份有限公司 | A kind of method for disinfection of recirculated cooling water and application |
| CN105819594A (en) * | 2015-01-09 | 2016-08-03 | 中国石油化工股份有限公司 | Recirculated cooling water processing method |
| CN115636479A (en) * | 2021-07-19 | 2023-01-24 | 重庆美的制冷设备有限公司 | Purifying equipment, control method and device thereof and storage medium |
| CN115636479B (en) * | 2021-07-19 | 2024-08-23 | 重庆美的制冷设备有限公司 | Purification device, control method and device thereof, and storage medium |
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